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US4339416A - Uranium recovery process - Google Patents

Uranium recovery process Download PDF

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US4339416A
US4339416A US06/094,889 US9488979A US4339416A US 4339416 A US4339416 A US 4339416A US 9488979 A US9488979 A US 9488979A US 4339416 A US4339416 A US 4339416A
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Prior art keywords
uranium
organic solvent
phosphoric acid
process according
phosphine oxide
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US06/094,889
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English (en)
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Richard Fitoussi
Claude Musikas
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents

Definitions

  • the present invention relates to a process for the recovery of the uranium present in phosphoric acid solutions and particularly in phosphoric acid solutions obtained from phosphatic ores.
  • phosphatic ores contain by no means negligible uranium quantities which, during the action of a sulphuric solution on these ores, pass into the phosphoric acid solution obtained.
  • the present invention relates to a process for the recovery of the uranium present in a phosphoric acid solution by means of organic solvents, making it possible to obtain good extraction levels and a satisfactory separation of the iron, even when the phosphoric acid concentration of the solution is relatively high, for example of the order of 8 M.
  • the invention therefore relates to a process for the recovery of the uranium present in a phosphoric acid solution by bringing the said solution into contact with an organic solvent suitable for extracting the uranium, wherein the said organic solvent comprises a system of extractants constituted by an acid organophosphorus compound having at least one sulphur atom and by a neutral phosphine oxide of formula: ##STR2## in which R 1 , R 2 and R 3 are identical or different alkyl, alkoxyalkyl or aryl radicals.
  • the acid organophosphorus compound having at least one sulphur atom is a dialkyl-dithiophosphoric acid such as di-2-ethylhexyl-dithiophosphoric acid, dibutyldithiophosphoric acid and bis-(2,6-dimethyl-4-heptyl)dithiophosphoric acid.
  • di-2-ethylhexyldithiophosphoric acid DEHDTP
  • DEHDTP di-2-ethylhexyldithiophosphoric acid
  • the neutral phosphine oxide used in accordance with the above formula is advantageously chosen from among the phosphine oxides in which R 1 , R 2 and R 3 are identical or different alkyl radicals having 4 to 12 carbon atoms, or from among phosphine oxides in which at least one of the radicals R 1 , R 2 or R 3 is an alkoxyalkyl radical with 4 to 12 carbon atoms, preferably with one alkoxymethyl radical, the other radicals being C 4 to C 12 alkyl radicals.
  • phosphine oxide which can be used reference is made to trioctyl phosphine oxide (TOPO) and di-n-hexyl-octyloxymethyl phosphine oxide (POX 11).
  • the process as defined hereinbefore utilises in an advantageous manner the nature of the organic solvent used.
  • a system of extractants constituted by said acid organophosphorus compound and by said neutral phosphine oxide makes it possible to obtain high uranium (VI) extraction coefficients and also ensure a separation of the iron and the uranium when the contacting time between the phosphoric acid solution and the organic solvent is limited to appropriate values or when a branches chain dialkyl dithiophosphoric acid is used, such as bis-(2,6-dimethyl-4-heptyl)-dithiophosphoric acid.
  • the above system of extractants is advantageously diluted in an inert solvent, such as dodecane.
  • the total concentration of extractants is preferably in excess of 0.6 M in order to obtain good uranium extraction levels.
  • the concentration of each of the extractants of the above system is advantageously such that the molar ratio of the neutral phosphine oxide to the acid organophosphorus compound having at least one sulphur atom is between 1/9 and 3/1 and preferably close to 1.
  • a complex is formed having one neutral phosphine oxide molecule and one acid organophosphorus compound molecule, which makes it possible to ensure uranium extraction under good conditions, because such a complex is neutral and the steric volume requirement in the equatorial plane of the UO 2 2+ ion enables it to be assumed that a complex is obtained with all its coordination sites occupied.
  • the organic solvent comprises an equimolar mixture of an acid organophosphorus compound having at least one atom of sulphur and a neutral phosphine oxide.
  • the uranium extracted in the organic solvent is then recovered by bringing the organic solvent into contact either with an aqueous phosphoric acid solution having a phosphoric acid concentration in excess of 10 M, or with an aqueous phosphoric acid solution containing a reducing agent for reducing uranium (VI) to uranium (IV).
  • process according to the invention can be performed in any conventional extraction apparatus, such as mixer-settler sets, pulsed columns, centrifugal extractors, etc.
  • FIG. 1 a diagram showing the variations in the partition coefficient D of uranium (VI) as a function of the composition of the organic solvent, i.e. the percentage of POX 11 or TOPO molecules in the system of extractants.
  • FIG. 2 a diagram showing the variations in the partition coefficient D of uranium (VI) and iron (III), as a function of the extraction period, when using a mixture of TOPO and DEHDTP as the solvent.
  • FIG. 3 a diagram showing the variations in the partition coefficient D of uranium (VI) and iron (III), as a function of the extraction period, when a mixture of POX 11 and DEHDTP is used as the solvent.
  • FIG. 4 a diagram showing the variations in the partition coefficient D of uranium (VI) as a function of the phosphoric acid concentration of the aqueous solution.
  • FIG. 5 a diagram showing the variations in the partition coefficient D of uranium (VI) as a function of the composition of the solvent, i.e. its concentration C (in M) of TOPO.
  • This example relates to the recovery of uranium present in a 5 M phosphoric acid solution containing 7.10 -4 mole per liter of uranium (VI).
  • DEHDTP di-2-ethylhexyldithiophosphoric acid
  • POX 11 di-n-hexyl-octyloxymethylphosphine oxide
  • Extraction is carried out by bringing into contact in a mixer one volume of the phosphoric acid solution and one volume of the organic solvent for about 30 minutes, whilst mechanically stirring the two phase present.
  • the two phases are then separated by centrifuging and are then sampled and analysed in order to determine the uranium concentration of each of these phases.
  • the uranium concentration is measured by a radiometric method, which implies that a radioactive tracer constituted by U 233 , which is an alpha emitter is added to the initial phosphoric solution.
  • the distribution or partition coefficient D is determined, this being equal to the ratio of the uranium concentration of the organic phase to the uranium concentration of the aqueous phase.
  • curve 1 of FIG. 1 illustrates the variation of the partition coefficient D as a function of the composition of the organic solvent, i.e. the percentage of the POX 11 molecule in the system of extractants.
  • partition coefficient D varies as a function of the composition of the organic solvent and that the partition coefficient has a maximum when using an equimolar mixture of DEHDTP and POX 11.
  • this partition coefficient has satisfactory values when the molar ratio of POX 11 to DEHDTP is between 1/9 and 3/1.
  • uranium is recovered from the same phosphoric acid solution as in example 1, using as the organic extraction solvent a mixture of di-2-ethylhexyl-dithiophosphoric acid (DEHDTP) and trioctyl-phosphine (TOPO) diluted in dodecane with a total concentration of extractants of 0.5 M/l, extraction being performed under the same conditions as in example 1.
  • DEHDTP di-2-ethylhexyl-dithiophosphoric acid
  • TOPO trioctyl-phosphine
  • the partition coefficient has a maximum when using an equimolar mixture of DEHDTP and TOPO.
  • the results are very satisfactory when the molar ratio of TOPO and DEHDTP is between 1/9 and 3/1.
  • the uranium is recovered from a 5 M phosphoric acid solution containing 0.17 g/liter of uranium and 3.4 g/liter of iron, using as the organic extraction solvent a mixture of 0.25 M/liter of TOPO and 0.25 M/liter of DEHDTP diluted in dodecane. Extraction is performed under the same conditions as in example 1, but by varying the contact time between the aqueous phase and the organic phase in order to determine the extraction kinetics of uranium (VI) and iron (III).
  • the partition coefficient D for the uranium and the partition coefficient D for the iron are then determined by measuring the uranium and iron concentrations of the aqueous phase and the organic phase by radiometric methods and whereby the radioactive traces added to the initial solution are uranium 233, which is an alpha emitter and iron 58, which is a gamma emitter.
  • FIG. 2 respectively illustrates the variations of D for iron and uranium as a function of the extraction time (enmn).
  • the uranium is covered from a 5 M phosphoric acid solution, which also contains 0.17 g/liter of uranium and 3.4 g/liter of iron, using a mixture of 0.25 M/liter of POX 11 and 0.25 M/liter of DEHDTP diluted in dodecane, the extraction being performed under the same conditions as in example 3, i.e. by varying the contacting time between the aqueous phase and the organic phase.
  • FIG. 3 illustrates the variations of D for uranium and iron as a function of the extraction period.
  • uranium is recovered from a phosphoric acid solution containing 7.10 -4 M/liter of uranium (VI), whilst using as the organic solvent a mixture of 0.25 M/l of TOPO and 0.25 M/l of DEHDTP diluted in dodecane, the extraction being performed under the same conditions as in Example 2. The D of the uranium is then determined for various phosphoric acid concentrations in the initial solution.
  • VI uranium
  • FIG. 4 illustrates the variations in D of uranium, as a function of the phosphoric acid concentration in the aqueous solution.
  • D decreases very rapidly when the H 3 PO 4 concentration exceeds 8 M and is not very high when the PO 4 H 3 concentration exceeds 10 M.
  • This example relates to the recovery of uranium from a 5 M phosphoric acid solution containing 0.17 g/l of uranium (VI) and 3.4 g/l of iron, using as the organic solvent a mixture of TOPO and DEHDTP diluted in dodecane.
  • Extraction is carried out in a centrifugal extractor with a contact time between two phases of the order of 4 seconds. After extraction the phases are separated and they are then analysed in order to determine the partition coefficients D of the uranium and the iron, as in example 3.
  • FIG. 5 illustrates the variations in the partition coefficient D of uranium (VI) as a function of the TOPO C concentrations (in moles) of the organic solvent.
  • FIG. 5 shows that good results are obtained even with a low DEHDTP concentration (0.01 M).
  • the partition coefficient increases with the TOPO concentration in the organic solvent.
  • a system of extractants constituted by an acid organophosphorus compound having at least one sulphur atom and by a neutral phosphine oxide extraction can be carried out under satisfactory conditions, i.e. relatively high uranium partition coefficients can be obtained, even when the mixture has a composition which is far removed from an equimolar mixture.
  • uranium reextraction can be subsequently carried out by contacting the uranium-containing organic solvent and a 1 M ammonium carbonate solution, because the low iron quantities extracted in the organic solvent will then remain in the organic phase.
  • This example relates to the extraction of uranium from a 6 M phosphoric acid solution containing 7.10 -4 M/l of uranium (VI).
  • the solvent used is a mixture of 0.25 M/l of DEHDTP and 0.25 M/l of TOPO diluted in dodecane or a mixture of 0.4 M/l of diethylhexyl phosphoric acid and 0.1 M/l of TOPO diluted in dodecane.
  • Uranium extraction takes place with each solvent system under the same conditions as in example 1 and at the end of the operation the distribution or partition coefficients D of the uranium are determined.

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  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
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  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US06/094,889 1978-11-28 1979-11-16 Uranium recovery process Expired - Lifetime US4339416A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7833544 1978-11-28
FR7833544A FR2442797A1 (fr) 1978-11-28 1978-11-28 Procede de recuperation de l'uranium present dans les solutions d'acide phosphorique

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JP (1) JPS5580723A (es)
AU (1) AU531420B2 (es)
CA (1) CA1143948A (es)
ES (1) ES8100352A1 (es)
FR (1) FR2442797A1 (es)
IL (1) IL58724A (es)
IT (1) IT1126404B (es)
MA (1) MA18654A1 (es)
ZA (1) ZA796295B (es)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4461747A (en) * 1982-01-13 1984-07-24 Commissariat A L'energie Atomique Method for separating actinides from lanthanides in an acidic aqueous solution
US4503016A (en) * 1981-07-15 1985-03-05 Hoechst Aktiengesellschaft Process for extracting heavy metal ions from aqueous solutions
US4867951A (en) * 1988-03-31 1989-09-19 The United States Of America As Represented By The United States Department Of Energy Separation of actinides from lanthanides
US4923630A (en) * 1988-03-31 1990-05-08 The United States Of America As Represented By The United States Department Of Energy Extractant composition
US20070075768A1 (en) * 2005-09-30 2007-04-05 Thomas Blon Circuit configuration having a feedback operational amplifier
RU2517651C1 (ru) * 2013-05-07 2014-05-27 Александра Валерьевна Ануфриева Способ экстракционной очистки нитратных растворов, содержащих рзм
RU2576763C1 (ru) * 2014-08-22 2016-03-10 Открытое акционерное общество "Научно-исследовательский институт двигателей" (ОАО "НИИД") Способ экстракционного разделения редкоземельных металлов из азотнокислых растворов
RU2611001C1 (ru) * 2016-03-04 2017-02-17 Акционерное общество "Ведущий проектно-изыскательский и научно-исследовательский институт промышленной технологии" (АО "ВНИПИпромтехнологии") Способ экстракционного разделения скандия и тория
RU2623943C1 (ru) * 2016-02-03 2017-06-29 Акционерное общество "Радиевый институт им. В.Г. Хлопина" Экстракционная смесь для извлечения тпэ и рзэ из высокоактивного рафината переработки оят аэс и способ её применения (варианты)
RU2626206C1 (ru) * 2016-09-22 2017-07-24 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Способ выделения скандия из концентратов редкоземельных элементов
RU2647047C1 (ru) * 2017-05-02 2018-03-13 Акционерное общество "Далур" Способ получения оксида скандия из концентрата скандия
RU2669737C1 (ru) * 2018-01-18 2018-10-15 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ получения оксида скандия из скандийсодержащих концентратов

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2478316A1 (fr) * 1980-03-17 1981-09-18 Commissariat Energie Atomique Procede de dosage d'uranium vi ou d'acide dialkyldithiophosphorique present dans un solvant organique
FR2486299A1 (fr) * 1980-07-03 1982-01-08 Commissariat Energie Atomique Procede de separation des actinides et des lanthanides presents a l'etat trivalent dans une solution aqueuse acide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858187A (en) * 1947-08-16 1958-10-28 Frederick T Fitch Uranium recovery
US3146064A (en) * 1952-08-29 1964-08-25 Robert L Moore Decontamination of uranium
US3243257A (en) * 1963-09-11 1966-03-29 Charles F Coleman Recovery of uranium and zirconium from aqueous fluoride solutions
US4012480A (en) * 1973-02-27 1977-03-15 Commissariat A L'energie Atomique Isotopic enrichment of uranium with respect to an isotope
US4243637A (en) * 1977-10-11 1981-01-06 Occidental Petroleum Company Uranium recovery from pre-treated phosphoric acid

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3737513A (en) * 1970-07-02 1973-06-05 Freeport Minerals Co Recovery of uranium from an organic extractant by back extraction with h3po4 or hf
SE398299B (sv) * 1976-04-21 1977-12-19 Berol Kemi Ab Forfarande och reagensblandning for avlegsnande av metalljoner ur en vattenlosning medelst vetskeextraktion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858187A (en) * 1947-08-16 1958-10-28 Frederick T Fitch Uranium recovery
US3146064A (en) * 1952-08-29 1964-08-25 Robert L Moore Decontamination of uranium
US3243257A (en) * 1963-09-11 1966-03-29 Charles F Coleman Recovery of uranium and zirconium from aqueous fluoride solutions
US4012480A (en) * 1973-02-27 1977-03-15 Commissariat A L'energie Atomique Isotopic enrichment of uranium with respect to an isotope
US4243637A (en) * 1977-10-11 1981-01-06 Occidental Petroleum Company Uranium recovery from pre-treated phosphoric acid

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4503016A (en) * 1981-07-15 1985-03-05 Hoechst Aktiengesellschaft Process for extracting heavy metal ions from aqueous solutions
US4461747A (en) * 1982-01-13 1984-07-24 Commissariat A L'energie Atomique Method for separating actinides from lanthanides in an acidic aqueous solution
US4867951A (en) * 1988-03-31 1989-09-19 The United States Of America As Represented By The United States Department Of Energy Separation of actinides from lanthanides
US4923630A (en) * 1988-03-31 1990-05-08 The United States Of America As Represented By The United States Department Of Energy Extractant composition
US20070075768A1 (en) * 2005-09-30 2007-04-05 Thomas Blon Circuit configuration having a feedback operational amplifier
RU2517651C1 (ru) * 2013-05-07 2014-05-27 Александра Валерьевна Ануфриева Способ экстракционной очистки нитратных растворов, содержащих рзм
RU2576763C1 (ru) * 2014-08-22 2016-03-10 Открытое акционерное общество "Научно-исследовательский институт двигателей" (ОАО "НИИД") Способ экстракционного разделения редкоземельных металлов из азотнокислых растворов
RU2623943C1 (ru) * 2016-02-03 2017-06-29 Акционерное общество "Радиевый институт им. В.Г. Хлопина" Экстракционная смесь для извлечения тпэ и рзэ из высокоактивного рафината переработки оят аэс и способ её применения (варианты)
RU2611001C1 (ru) * 2016-03-04 2017-02-17 Акционерное общество "Ведущий проектно-изыскательский и научно-исследовательский институт промышленной технологии" (АО "ВНИПИпромтехнологии") Способ экстракционного разделения скандия и тория
RU2626206C1 (ru) * 2016-09-22 2017-07-24 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Способ выделения скандия из концентратов редкоземельных элементов
RU2647047C1 (ru) * 2017-05-02 2018-03-13 Акционерное общество "Далур" Способ получения оксида скандия из концентрата скандия
RU2669737C1 (ru) * 2018-01-18 2018-10-15 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Способ получения оксида скандия из скандийсодержащих концентратов

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ES486077A0 (es) 1980-11-01
IL58724A (en) 1982-12-31
IT7927607A0 (it) 1979-11-27
CA1143948A (en) 1983-04-05
FR2442797B1 (es) 1982-10-15
FR2442797A1 (fr) 1980-06-27
JPS5580723A (en) 1980-06-18
MA18654A1 (fr) 1980-07-01
AU531420B2 (en) 1983-08-25
ZA796295B (en) 1981-08-26
ES8100352A1 (es) 1980-11-01
IT1126404B (it) 1986-05-21
AU5294579A (en) 1980-05-29

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